Detergent composition for the hair



United States Patent Switzerland No Drawing. Filed July 18, 1955, Ser. No. 522,823 Claims priority, application Switzerland July 20, 1954 8 Claims. (Cl. 252-152) It is known that cation-active compounds can be used for making detergent preparations for the hair. As compared with anion-active detergents they have in general the advantage that the properties of the hair are favorably infiuenced. The feel, softness and combability of the hair are considerably improved. The hair acquires a beautiful gloss, and weakened and attacked hair is rendered ,firm so that the further treatment is facilitated.

Cation-active compounds tend to have the disadvantage that they cause certain irritant phenomena in persons having very sensitive skin. The present invention is based on the observation that this disadvantage is avoided or very considerably reduced by using cationactive detergents together with water-soluble non-ionic compounds which are derived from non-aromatic mercaptans.

Accordingly, the invention provides cation-active detergents for the hair, which contain (a) at least one compound free from imidazoline rings and containin at least one basic nitrogen atom and at least one non-aromatic radical containing more than 6 carbon atoms. in the form of a water-soluble salt or a water-soluble guaternary ammonium salt and at least one water-soluble non-ionic compound derived from a mercapto-compound containing a non-aromatic radical of at least 10 carbon atoms. As cation-active compounds there may be used any compounds suitable as detergents for the hair, provided that they contain no imidazoline rings. There come into consideration amine salts and quaternary ammonium salts. It is especially advantageous to use compounds whose salts give strongly foaming solutions in water. There may be mentioned, for example, the following compounds, lauroylamido-ethyl-pyridinium sulfate, the lauroyl ester of dimethyl-ethanolamine hydrochloride, the lauroyl ester of triethanolamine hydrochloride, octadecylpyridinium bromide, dimethyl-octadecyloxy-ethyl-ammonium chloride, stearoylamido-ethylene-trimethyl-ammonium methyl sulfate, or the lactate of the amide of trihydroxyethyl-ethylene diamine and lauric acid corresponding to the formula On account of their good cleansing and foaming properties it is of advantage to use compounds containing an aliphatic hydrocarbon radical of 12-14 carbon atoms, for example, a salt of a lauroyl-ethylene diamine, of which the lauroyl radical is bound to an NH- group of the ethylene diamine radical.

The non-ionic water soluble aliphatic mercaptan derivatives may be derived, for example, from dodecylmercaptan, hexadecyl mercaptan or octadecyl mercaptan. There are advantageously used alkylene oxide condensation products, especially ethylene oxide condensation products. An especially suitable product is the compound obtainable from tertiary dodecylrnercaptan and ethylene oxide, of which the turbidity point of a solution of 0.115% strength is about 69 C. and whose refractive index is 1.4685 for the D-line.

It is of advantage to impart to the detergent compositions of the invention an acid reaction. The pH-value 2,992,994 Patented July 18, 1961 may be suitably adjusted by adding a compound of acid reaction. As such compounds there may be used salts of acid reaction, such as primary phosphates. Advantageously, however, there are used the organic acids customarily used for this purpose in cosmetics, for example, aliphatic hydroxy-carboxylic acids, such as glycollic acid or citric acid, but especially lactic acid.

' The detergent preparations of the invention can be made by simple mixing and dissolutions of the components. A single member of each class may be used or a mixture of two or more compounds of one or both classes. There may also be added compounds customarily used in detergent preparations for the hair, such as perfume, dyestufis, bleaching agents or thickening agents. It is especially advantageous to add fatty acid alkanolamides, for example, coconut oil fatty acid hydroxyethylamide. The new preparations may be made up in solid, pastelike or liquid form. They are used in known manner for the treatment of the hair. The hair so treated is generally well defatted, acquires a soft feel and beautiful gloss, and can be easily brushed because its tendency to become electrostatically charged is reduced.

The following examples illustrate the invention, the parts being by weight:

Example 1 10 parts of the lactate of N:N-dimethyl-ethanolamine esterified with coconut oil fatty acid are mixed with 10 parts of a water-soluble condensation product of tertiary dodecyl mercaptan with ethylene oxide, for example, the condensation product of 1 molecular proportion of tertiary dodecyl mercaptan with 8-10 molecular proportions of ethylene oxide, and parts of water.

Among the above-mentioned condensation products of tertiary dodecyl mercaptan with ethylene oxide there is especially suitable the product of which the turbidity point of a solution of 0.115 percent strength is about 69 C. The refractive index of this condensation product is 1.4685 for the D-line.

Example 2 21.6 parts of the amide of trihydroxyethyl-ethylene diamine and lauric acid described below are mixed with 14.7 parts of lactic acid of about percent strength, 7.85 parts of a water-soluble condensation product of tertiary dodecyl mercaptan with ethylene oxide (for example, the product of which the turbidity point of a solution of 0.115 percent strength is about 69 C.), 4.9 parts of N-hydroxyethyl-coconut oil fatty acid amide, 2 parts of para (stearoylamino) phenyl trimethylammonium methosulfate and 49 parts of water.

The above mentioned amide of trihydroxyethyl-ethylene diamine and lauric acid may be prepared as follows:

Ethylene oxide is introduced through a glass frit at a reaction temperature of 65-100 C. into 90 parts of ethylene diamine until the increase in weight amounts to 200 parts.

The colorless liquid is fractionated, and there is obtained in a yield of about 75 percent trihydroxyethylethylene diamine in the form of a colorless liquid boiling at 183-192 C. under 0.15 mm. pressure.

200 parts of lauric acid and 198 parts of trihydroxyethyl-ethylene diamine are heated under a pressure of 50-60 mm. of mercury in a current of nitrogen, first for one hour at C. and then for 7 hours at C. The water formed by the reaction is distilled off as it is formed. There is obtained a clear brown oil which yields with water opalescent solutions that foam well. With dilute acid it forms clear solutions that foam well.

Example 3 The procedure is the same a described in Example 2 3 except that there is used, instead of the amide of trihydroxyethyl-ethylene diamine and lauric acid described therein, NzN-dimethyl-ethanolamine esterified with coconut oil fatty acid.

Example 4 The procedure is the same as described in Example 2, except that there is used, instead of the amide of trihydroxyethyl-ethylene diamine and lauric acid described therein, the same quantity of triethanolamine mono-coconut oil fatty acid ester. This ester can be obtained in the usual manner from triethanolamine and coconut oil fatty acid.

Example 5 The procedure is the same as described in Example 2, except that there is used, instead of the amide of trihydroxyethyl-ethylene diamine and lauric acid described therein, the same quantity of the condensation product obtained as follows:

126.6 parts of coconut oil fatty acid amide, 25.9 parts of paraformaldehyde of 96.4 percent strength, 98.2 parts of triethanolamine and 3.2 parts of anhydrous sodium carbonate are heated together in a current of nitrogen, while stirring, for 3 hours at 60-65 C. The whole is then stirred for 2 hours in a bath at 80-85 C., 1.2 parts of boric acid are added, and the whole is stirred for a further 4 hours under reduced pressure at an internal temperature of 130-132" C. During the first M: hour the pressure is maintained at 560 mm., during the next 2% hours at 360 mm. and during the last hour at about 12 mm.

The condensation product so obtained is clearly soluble in dilute lactic acid.

Example 6 The procedure is the same as described in Example 2, except that there is used instead of the amide of trihydroxyethyl-ethylene diamine and lauric acid described therein, the ester obtained in the manner described below.

30.5 parts of monoethanolamine are heated to 110 C. in a current of nitrogen and then propylene oxide is introduced at 110-130" C. in the form of a finely distributed gas stream until the increase in weight amounts to 116 parts. The speed of the reaction, which becomes slow after about 64 parts of propylene oxide have been taken up, is advantageously increased by adding 0.1 part of metallic sodium.

64.5 parts of the hydroxypropylated amine so obtained are heated in a current of nitrogen to 140 C., and then 42.4 parts of distilled coconut oil fatty acid are introduced into the reaction vessel in the course of about 2 hours. This is advantageously carried out while passing nitrogen through the apparatus. The whole is then stirred for 5 hours in a current of nitrogen at a bath temperature of 170-175 C. and finally for a further 2 hours at the same temperature under reduced pressure produced by a water jet pump. The lactate of the ester so obtained is clearly soluble in water.

Example 7 10 parts of hydroxyethylaminoethyl-lauroyl amide are mixed with 7.5 parts of lactic acid of 90 percent strength, 4 parts of a water-soluble condensation product of tertiary dodecyl mercaptan with ethylene oxide (for example, the product of which the turbidity point in a solution of 0.115 percent strength is about 69 C.), 2.5 parts of coconut oil fatty acid hydroxyethylamide, 1 part of para (stearoylamino) phenyl trimethyl-ammonium methosulfate and parts of water.

A detergent preparation of this composition has a very good foaming and washing action and is practically unchanged after being heated for 72 hours at 50 C.

The hydroxyethylaminoethyl-lauroylamide may be prepared as follows: 160 parts of lauric acid, 85 parts of hydroxyethyl-ethylene diamine, 1.5 parts of boric acid 4 and 300 parts of xylene are gently heated, while stirring, until dissolution is complete, and then the mixture is heated at the boil.

After about 5 hours about 16 parts of water have been eliminated and the residue from an evaporated test portion is clearly soluble in dilute acid. The xylene solution is then concentrated in vacuo, whereby a yellow residue is obtained, which solidifies in a short time to a pale yellow mass. The hydroxyethylaminoethyl-lauroylamide can be stirred in water to give a turbid emulsion.

By the addition of a small amount of acid there is obtained a clear solution that foams well.

If, however, the product is heated at the boil for more than 5 hours, the second molecular proportion of water splits off and the corresponding imidazoline derivative is obtained.

Instead of lauric acid, there may be used coconut oil fatty acid without diminishing the foaming power of the product. A

Example 8 A detergent preparation for the hair is made in the manner described in Example 7, except that there is used instead of the hydroxyethylaminoethyl-lauroylamide, 10 parts of the reaction product obtained as follows.

28.6 parts of hydroxyethylaminoethyl-lauroylamide, 9 parts of a-chlorhydrin and 100 parts of ethanol are heated for 6 hours under reflux. The mixture is cooled, and then stirred with 4 parts of powdered sodium hydroxide, the precipitated sodium chloride is filtered off, and the solution is concentrated. The ochre colored paste can be stirred with water to yield an opalescent solution that foams easily. With dilute acid there is obtained a clear solution that foams well.

Example 9 A detergent preparation is made in the manner described in Example 7, except that there is used, instead of the hydroxyethylaminoethyl-lauroylamide, 10 parts of the reaction product obtained as follows:

A preparation of this composition possesses a very good foaming and washing action and is practically unchanged after being heated for 72 hours at 50 C. 28.6 parts of hydroxyethylaminoethyl-lauroylamide, 9.5 parts of chloracetamide and 100 parts of ethanol are heated for 5 hours under reflux. The whole is stirred in the cold with 4 parts of pulverized sodium hydroxide, filtered to remove precipitated sodium chloride, and concentrated. The pale brown paste is clearly soluble in water. With dilute acids it forms clear strongly foaming solutions.

Example 10 28.6 parts of hydroxyethylaminoethyl-lauroylamide, 9.5 parts of chloracetic acid and 38 parts of water are heated at C., while stirring. After 5 hours a test portion is clearly soluble in water to give solutions that foam well.

In order to prepare a detergent preparation for the hair, 26 parts of the above hydrochloride solution are mixed with 4 parts of lactic acid of percent strength, 4 parts of a water-soluble condensation product of tertiary dodecylmercaptan with ethylene oxide (for example, the product of which the turbidity point of a solution of 0.115 percent concentration is about 69 C.), 2.5 parts of coconut oil fatty acid hydroxyethylamide, 1 part of para- (stearoylamino)-phenyl-trimethyl-ammonium methosulfate and 13 parts of water.

A detergent preparation of this composition has a very good washing and foaming action.

Example 11 tion of 0.115 percent strength is about 69 C.), 1 part of coconut oil fatty acid hydroxyethylamide, 1 part of para- (stearoylamino)-phenyl-trimethyl-ammonium methosulfate and 25 parts of water.

There is obtained a pale stable paste, which, when used as a detergent preparation for the hair, has a good foaming power and an excellent washing action. Hair which has been treated therewith has an especially soft feel, a beautiful gloss and a good capacity for being dressed.

Instead of hydroxyethylaminoethyl-stearoylamide, there may be used a mixture of the corresponding lauroyland stearoyl-compounds.

The hydroxyethylaminoethyl-stearoylamide can be prepared as follows:

284 parts of stearic acid, 106 parts of hydroxyethylethylene diamine, 1.5 parts of boric acid and 400 parts of xylene are heated, while stirring until dissolution is complete. The mixture is then heated at the boil. After about 5 hours 18-19 parts of water have been eliminated, and the residue from an evaporated test portion is almost clearly soluble in dilute acid. The xylene solution is evaporated in vacuo, whereby a yellow residue is obtained which solidifies in a short time to a pale hard mass.

Example 12 13 parts of the reaction product described below are mixed with 4 parts of a water-soluble condensation product of tertiary dodecylmercaptan with ethylene oxide (for example, the product of which the turbidity point of a solution of 0.115 percent strength is about 69 C.), 1 part of coconut oil fatty acid hydroxyethylamide, 1 part of para-(stearoylamino)-phenyl-trimethyl-ammonium methosulfate and 31 parts of water.

The detergent preparation for the hair so obtained is a pale stable paste, which, in addition to developing foam well, has an extraordinarily good washing action.

The reaction product used is prepared by reacting hydroxyethylaminoethyl-stearoylamide in the manner described in Example 3 with chloracetamide and liberating the base with the addition of sodium hydroxide.

The base forms turbid foaming solutions with water and with dilute acids.

The above described detergent preparation may contain with advantage, instead of the stearoyl-compound, a mixture of the corresponding lauroyl and stearoylcompounds.

Example 13 A detergent preparation for the hair is made in the manner described in Example 11, except that there is used, instead of the hydroxyethylaminoethyl-stearoylamide, 13 parts of the reaction product prepared as follows:

A preparation of this composition has a good foaming and washing action. Hydroxyethylaminoethyl-stearoylamide is reacted in the manner described in Example 2 with a-chlorhydrin, and finally the base is liberated. Instead of a-chlorhydrin, there may be used ethylene chlorhydrin. The resulting reaction products are pale firm pastes, which yield turbid foaming solutions with acids.

The washing capacity of the above described detergent preparation may be increased by adding, instead of lactic acid, the same quantity of water. At the same time the foam formed is softer and more abundant.

Example 14 74 parts of hydroxyethylaminoethyl-stearoylamide, 19 parts of monochloracetic acid and 93 parts of water are heated at 70-80" C., while stirring. After about 4 hours a test portion is clearly soluble in water to give a good foaming solution.

In order to make a detergent preparation for the hair, 28 parts of the above hydrochloride solution are mixed with 4 parts of a water-soluble condensation product of tertiary dodecylmercaptan with ethylene oxide (for example, the product of which the turbidity point of a so lution of 0.115 percent strength is about 69 C.), 1 part of coconut oil fatty acid hydroxyethylamide, 1 part of para-(stearoylamino)-phenyl-trimethyl-ammonium methosulfate and 16 parts of water.

A detergent preparation of this composition has a very good washing and foaming action.

Example 15 21.6 parts of the quaternary ammonium salt described below are mixed with 7 parts of lactic acid of about percent strength, 7.85 parts of a water-soluble condensation product of tertiary dodecylmercaptan with ethylene oxide (for example, the product of which the turbidity point of a solution of 0.115 percent strength is about 69 C.), 4.9 parts of N-hydroxyethyl-coconut oil fatty acid, 2 parts of para-(stearoylamino)-phenyl-trimethyl ammonium methosulfate and 56 parts of water.

The quaternary ammonium salt referred to above is prepared as follows:

28.3 parts of N:N-dimethyl-ethanolamine esterified with coconut oil fatty acid and 10.3 parts of chloracetic acid amide are heated in a current of nitrogen on the boiling water bath, while stirring, until the reaction product is clearly soluble in water, which is the case in a short time.

Example 16 A detergent preparation for the hair is prepared by mixing 2 parts of hydroxyethylaminoethyl-coconut oil fatty acid amide, 3 parts of hydroxyethylaminoethylstearic acid amide, 1 part of coconut oil fatty acid ethanolamide, 12 parts of the condensation product obtained from hexadecylmercaptan and ethylene oxide as described below, 2 parts of lactic acid and 80 parts of water.

A detergent preparation of this composition has an excellent washing action.

The condensation product from tertiary hexadecyl mercaptan and ethylene oxide referred to above may be prepared as follows:

20 parts of tertiary hexadecylmercaptan and 0.1 part of sodium are heated in a current of nitrogen to C. Ethylene oxide is then passed in in the form of a finely distributed gas stream until 50 parts have been taken up at l40l50 C. A solution of 1 percent strength of the oxyethylation product so obtained has a turbidity point of about 56 C.

Example 17 A detergent preparation for the hair is prepared by mixing 5 parts of dihydroxyethylaminoethyl-stearic acid amide, 1 part of coconut oil fatty acid ethanolamide, 12 parts of the condensation product from tertiary dodecyl mercaptan and ethylene oxide described below, and 81 parts of water.

A detergent preparation having this composition has an excellent washing action.

The condensation product described above from dodecyl mercaptan and ethylene oxide can be prepared as follows:

30 parts of tertiary dodecylmercaptan are mixed with 0.05 part of sodium and heated in a current of nitrogen at 140 C. Ethylene oxide is then passed in in the form of a finely distributed gas stream at 140-150 C. until 72 parts 'have been taken up. A solution of 1 percent strength of the condensation product so obtained has a turbidity point of about 56 C.

Example 18 In order to wash living hair a solution of 20 parts of the preparation described in the first paragraph of Example 1 or in the first paragraph of Example 7 in 80 parts of warm water is prepared. The hair washed with this strongly foaming solution of acid reaction is well defatted and has, in addition to a beautiful gloss, a pleasant soft feel. Moreover, the tendency for the hair to become electrostatically charged during brushing is considerably reduced.

What is claimed is:

l. A cosmetic detergent composition for the hair, which comprises (a) at least one cation-active detergent compound free from imidazoline rings and containing at least one basic nitrogen atom and at least one aliphatic hydrocarbon radical of more than 6 carbon atoms in the form of a water-soluble salt and (b) a water-soluble condensation product of tertiary dodecyl mercaptan and ethylene oxide, the proportion of said condensation product being sufficient to counteract the skin-irritating effect of the cation-active detergent in said cosmetic detergent composition.

2. A cosmetic detergent composition for the hair, which comprises (a) at least one cation-active detergent compound free from imidazoline rings and containing at least one basic nitrogen atom and at least one aliphatic hydrocarbon radical having 12 to 18 carbon atoms in the form of a water-soluble salt and (b) a watersoluble condensation product of tertiary dodecyl mercaptan and ethylene oxide, the proportion of said condensation product being sufiicient to counteract the skinirritating effect of the cation-active detergent in said cosmetic detergent composition.

3. A cosmetic detergent composition for the hair, which comprises (a) at least one cation-active detergent compound free from imidazoline rings and containing at least one basic nitrogen atom and at least one aliphatic hydrocarbon radical having 12 to 18 carbon atoms in the form of a water-soluble salt yielding a strongly foaming aqueous solution, (b) a'water-soluble condensation product of tertiary dodecyl mercaptan and ethylene oxide and (c) a cosmetically acceptable compound of acid reaction, the proportion of said condensation product being sufficient to counteract the skin-irritating elfect of the cation-active detergent in said cosmetic detergent composition.

4. A cosmetic detergent composition for the hair, which comprises (a) lactate of NzN-dimethyl-ethanol-amine coconut oil fatty acid ester, and (b) condensation product of tertiary dodecyl mercaptan and ethylene oxide of which the turbidity point of an aqueous solution of 0.115 percent strength is 69 C. and whose refractive index for the D-line is 1.4685, the proportion of said condensation product being suificient to counteract the skin-irritating efiect of the cation-active detergent in said cosmetic detergent composition.

5. A cosmetic detergent composition for the hair, which comprises (a) lactate of the amide of trihydroxyethylethylene diamine and lauric acid, (b) condensation product of tertiary dodecyl mercaptan and ethylene oxide of which the turbidity point of an aqueous solution of 0.115 percent strength is 69 C. and whose refractive index for the D-line is 1.4685, (c) lactic acid, (d) N-hydroxyethylcoconut oil fatty acid amide, and (e) para-(stearoylamino)-phenyl-trimethylammonium methosulfate, the proportion of said condensation product being sufiicient to counteract the skin-irritating effect of the cation-active detergent in said cosmetic detergent composition.

6. A cosmetic detergent composition for the hair, which comprises (a) lactate of triethanolarnine mono-coconut oil fatty ester, (b) condensation product of tertiary dodecyl mercaptan and ethylene oxide of which the turbidity point of an aqueous solution of 0.115 percent strength is 69 C. and whose refractive index for the D-line is 1.4685, (c) lactic acid, (d) N-hydroxyethylcoconut oil fatty acid amide, and (e) para-(stearoylamino)-phenyl-trimethylammonium methosulfate, the proportion of said condensation product being suflicient to counteract the skin-irritating effect of the cation-active detergent in said cosmetic detergent composition.

7. A cosmetic detergent composition for the hair, which comprises (a) di-(hydroxyethyl)-aminoethyl-stearic acid amide, (b) condensation product of tertiary dodecyl mercaptan and acid. ethylene oxide of which the turbidity point of an aqueous solution of 1 percent strength is about 56 C., and (c) N-hydroxyethyl-coconut oil fatty acid amide, the proportion of said condensation product being sufiicient to counteract the skin-irritating effect of the cation-active detergent in said cosmetic detergent composition.

8. A cosmetic detergent composition for the hair, which comprises (a) hydrochloride of the condensation product of hydroxyethylaminoethyl-stearoyl amide and monochloracetic acid, (b) condensation product of tertiary dodecyl mercaptan and ethylene oxide of which the turbidity point of an aqueous solution of 0.115 percent strength is 69 C. and whose refractive index for the D-line is 1.4685, (c) N-hydroxyethyl-coconut oil fatty acid amide, and (d) para-(stearoylamino)-phenyl-trimethylammonium methosulfate, the proportion of said condensation product (b) being suflicient to counteract the skin-irritating effect of the cation-active detergent in said cosmetic detergent composition.

References Cited in the file of this patent UNITED STATES PATENTS 2,103,872 Schoeller et al. Dec. 28, 1937 2,340,881 Kelley et al. Feb. 8, 1944 2,540,678 Kelley Feb. 6, 1951 2,543,852 Jaccard Mar. 6, 1951 2,577,503 Barid et al. Dec. 4, 1951 2,601,329 Sanders et al. June 24, 1952 2,669,546 Zussman et al. Feb. 16, 1954 2,703,795 Carpenter Mar. 8, 1955 2,709,178 Schlapfer et a1 May 24, 1955 2,724,699 Barker Nov. 22, 1955 2,755,252 Fong et al July 17, 1956 FOREIGN PATENTS 730,279 Great Britain May 18, 1955 1,029,221 France Mar. 4, 1953 743,177 Germany Dec. 20, 1943 OTHER REFERENCES Stupel: Manufacturing Chemist, March 1952, pp. 99- 102.

Surface Active Agents, by Schwartz et al., pub. by Interscience Publishers, Inc., N.Y. (1949), pp. 173, 181, 182, 206, 208, 212, 213.

Synthetic Detergents, by McCutcheon, pub. by MacNair Dorland Co., N.Y. (1950), pp. 292, 321, 322. 

1. A COSMETIC DETERGENT COMPOSITION FOR THE HAIR, WHICH COMPRISES (A) AT LEAST ONE CATION-ACTIVE DETERGENT COMPOUND FREE FROM IMIDAZOLINE RINGS AND CONTAINING AT LEAST ONE BASIC NITROGEN ATOM AND AT LEAST ONE ALIPHATIC HYDROCARBON RADICAL OF MORE THAN 6 CARBON ATOMS IN THE FORM OF A WATER-SOLUBLE SALT AND (B) A WATER-SOLUBLE CONDENSATION PRODUCT OF TERTIARY DODECYL MERCAPTAN AND ETHYLENE OXIDE, THE PROPORTION OF SAID CONDENSATION PRODUCT BEING SUFFICIENT TO COUNTERACT THE SKIN-IRRITATING EFFECT OF THE CATION-ACTIVE DETERGEN IN SAID COSMETIC DETERGENT COMPOSITION. 